WO2017068324A1 - Buoyancy component including dicyclopentadiene resin - Google Patents

Buoyancy component including dicyclopentadiene resin Download PDF

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Publication number
WO2017068324A1
WO2017068324A1 PCT/GB2016/053118 GB2016053118W WO2017068324A1 WO 2017068324 A1 WO2017068324 A1 WO 2017068324A1 GB 2016053118 W GB2016053118 W GB 2016053118W WO 2017068324 A1 WO2017068324 A1 WO 2017068324A1
Authority
WO
WIPO (PCT)
Prior art keywords
macrospheres
component
mould
buoyancy
microspheres
Prior art date
Application number
PCT/GB2016/053118
Other languages
English (en)
French (fr)
Inventor
Simon Harry Shepherd
David HAMNETT
Original Assignee
Advanced Insulation Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Advanced Insulation Plc filed Critical Advanced Insulation Plc
Priority to DK16788184.6T priority Critical patent/DK3362506T3/da
Priority to KR1020187014212A priority patent/KR20180083338A/ko
Priority to PL16788184T priority patent/PL3362506T3/pl
Priority to EP16788184.6A priority patent/EP3362506B1/en
Priority to US15/769,604 priority patent/US10676584B2/en
Priority to BR112018007984-7A priority patent/BR112018007984B1/pt
Publication of WO2017068324A1 publication Critical patent/WO2017068324A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/58Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
    • B29C70/66Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres the filler comprising hollow constituents, e.g. syntactic foam
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46Ruthenium, rhodium, osmium or iridium
    • B01J23/462Ruthenium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/16Solid spheres
    • C08K7/18Solid spheres inorganic
    • C08K7/20Glass
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/08Copolymers of styrene
    • C08L25/12Copolymers of styrene with unsaturated nitriles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L1/00Laying or reclaiming pipes; Repairing or joining pipes on or under water
    • F16L1/12Laying or reclaiming pipes on or under water
    • F16L1/20Accessories therefor, e.g. floats, weights
    • F16L1/24Floats; Weights
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3325Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40Polymerisation processes
    • C08G2261/41Organometallic coupling reactions
    • C08G2261/418Ring opening metathesis polymerisation [ROMP]
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02Homopolymers or copolymers of hydrocarbons
    • C08J2425/04Homopolymers or copolymers of styrene
    • C08J2425/08Copolymers of styrene
    • C08J2425/12Copolymers of styrene with unsaturated nitriles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/40Glass

Definitions

  • This invention concerns a method of forming a buoyancy providing component, and a buoyancy providing component.
  • Buoyancy providing materials and components are required in a wide range of fields.
  • One such field is the oil and gas production industry.
  • distributed buoyancy modules are often required which can comprise subsea floats applied to flexible subsea pipelines to provide buoyancy to offset the weight of the products in water.
  • Such floats would be distributed at specific locations along the pipe. Buoyancy may also be provided at other locations.
  • Such foams generally comprise glass or thermoplastic microspheres in an epoxy or polyurethane resin.
  • Epoxy resin has a relatively high viscosity even when mixed with a hardener, which limits the amount of filler i.e. microspheres, which can be contained therein, until the material becomes too viscous to be workable.
  • the setting of epoxy resin is exothermic and tends to have a peak exotherm of over 150°C. This can cause damage if for instance thermoplastic fillers or components are used.
  • the resulting cured syntactic foam usually has a high strength and stiffness but does tend to be brittle.
  • Polyurethane tends to be a little less viscous than epoxy resins, but still not particularly easy to handle or mix. Also it tends to have a lower exotherm than epoxy resins. However, the resultant syntactic foam is not as strong or stiff as epoxy syntactic foam. This means that it does not reinforce the microspheres as much, such that more individual microspheres may implode if a higher grade of microspheres is not used. Higher grade microspheres though generally have a greater density and therefore provide less buoyancy.
  • a method of forming a buoyancy providing component comprising locating a plurality of macrospheres in a mould, providing a composition including DCPD (dicyclo pentadiene) resin, a ruthenium or osmium catalyst, and a plurality of microspheres, dispensing the composition in liquid form into the mould to encapsulate the macrospheres, and allowing the mixture to set in the mould.
  • DCPD diclo pentadiene
  • the mould may form part of the buoyancy providing component, and may form an external shell for the component.
  • the catalyst may be ruthenium.
  • the macrospheres may have a diameter of greater than 20mm, may have a diameter of greater than 40mm, may be greater than 50mm, and may have a diameter of approximately 55mm.
  • the volume of macrospheres in the component may be greater than 50%, and may be between 50 and 60%.
  • the macrospheres may have a density of between 0.2 and 0.6gcm "3 .
  • the macrospheres may be formed by injection moulding, and may be formed in two halves which are subsequently bonded together.
  • the macrospheres may be formed of a glass fibre filled thermoplastic compound, and may be formed of glass reinforced styrene acrylonitrile thermoplastic material.
  • the internal volume of the macrospheres may be less than 100cm 3 , and may be less than 90cm 3 .
  • the microspheres may be glass microspheres.
  • the microspheres may form between 50 and 70% by volume of the composition.
  • buoyancy aiding component the component being made by a method according to any of the preceding eleven paragraphs.
  • a distributed buoyancy module component is made as follows.
  • a DCPD resin is mixed with a ruthenium catalyst and between 50 and 70% by volume glass microspheres to form a settable composition.
  • An appropriate glass microsphere would be a Scotchlite ® K20 product available from 3M.
  • the settable composition is dispensed to encapsulate the macrospheres, such that the macrospheres make up approximately 60% of the volume of the material in the mould.
  • the material is then left to set, such that the component is formed from a plurality of macrospheres in a syntactic foam matrix.
  • the set material is subsequently removed from the mould.
  • the mould forms the outer shell of the component, and the material once set is retained in the mould.
  • the resultant component is found to provide a very high stiffness. This high stiffness allows lighter grades of microspheres to be used, than would be the case with other materials. With the relatively low exotherm during curing of the DCPD, thermoplastic material macrospheres can be used, without substantial damage occurring to them during curing of the DCPD, even with the DCPD being dispensed in a single step.
  • the material used in the component is capable of providing buoyancy at a depth of at least 2000m subsea without failure.
  • the microspheres are reinforced by the high stiffness DCPD.
  • the macrospheres are made by injection moulding two hemispheres using glass reinforced styrene acrylonitrile engineering thermoplastic material. The two hemispheres are subsequently bonded together to form a hollow sphere.
  • buoyancy providing component material usable in forming such components which provides a number of advantages.
  • the use of DCPD relative to for instance epoxy and polyurethane provides advantages in that it has a lower viscosity making it easier to handle and mix, and also meaning that a larger volume of filler can be provided.
  • the higher volume of filler provides for increased buoyancy meaning that components with greater buoyancy are provided and/or potentially smaller components can be used. This also provides a saving in costs in production, handling and storage etc.
  • the DCPD is quite workable during production due to its low viscosity, and also has a relatively low exotherm during production, thereby allowing thermoplastic macrospheres to be used which otherwise could be damaged by a higher exotherm, even if the DCPD is dispensed in a single operation.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
PCT/GB2016/053118 2015-10-22 2016-10-06 Buoyancy component including dicyclopentadiene resin WO2017068324A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DK16788184.6T DK3362506T3 (da) 2015-10-22 2016-10-06 Opdriftskomponent, der omfatter dicyclopentadien-resin
KR1020187014212A KR20180083338A (ko) 2015-10-22 2016-10-06 부력 컴포넌트
PL16788184T PL3362506T3 (pl) 2015-10-22 2016-10-06 Element zapewniający pływalność zawierający żywicę dicyklopentadienową
EP16788184.6A EP3362506B1 (en) 2015-10-22 2016-10-06 Buoyancy component including dicyclopentadiene resin
US15/769,604 US10676584B2 (en) 2015-10-22 2016-10-06 Buoyancy component including dicyclopentadiene resin
BR112018007984-7A BR112018007984B1 (pt) 2015-10-22 2016-10-06 Método de formação de um componente de fornecimento de flutuabilidade e componente auxiliar de flutuabilidade

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1518745.3A GB201518745D0 (en) 2015-10-22 2015-10-22 Buoyancy component
GB1518745.3 2015-10-22

Publications (1)

Publication Number Publication Date
WO2017068324A1 true WO2017068324A1 (en) 2017-04-27

Family

ID=55130089

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2016/053118 WO2017068324A1 (en) 2015-10-22 2016-10-06 Buoyancy component including dicyclopentadiene resin

Country Status (8)

Country Link
US (1) US10676584B2 (ko)
EP (1) EP3362506B1 (ko)
KR (1) KR20180083338A (ko)
BR (1) BR112018007984B1 (ko)
DK (1) DK3362506T3 (ko)
GB (1) GB201518745D0 (ko)
PL (1) PL3362506T3 (ko)
WO (1) WO2017068324A1 (ko)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111875730B (zh) * 2020-08-17 2022-03-18 台州中浮新材料科技股份有限公司 一种高性能固体浮力材料及其制备方法
CN112521706B (zh) * 2020-12-04 2022-08-02 广东聚航新材料研究院有限公司 一种深海固体浮力材料及其制备方法
WO2022132145A1 (en) * 2020-12-17 2022-06-23 Halliburton Energy Services, Inc. Weight and density stable materials for flow control device float bodies

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622437A (en) * 1969-05-09 1971-11-23 Gen Dynamics Corp Composite buoyancy material
US5082726A (en) * 1989-11-01 1992-01-21 Grace N.V. Internal manifold that aids in filling molds
WO1999005447A1 (en) * 1997-07-23 1999-02-04 Cuming Corporation Subsea pipeline insulation
US6525125B1 (en) * 1999-02-05 2003-02-25 Materia, Inc. Polyolefin compositions having variable density and methods for their production and use

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7285593B1 (en) * 1998-05-19 2007-10-23 Advanced Polymer Technologies, Inc. Polyolefin compositions optionally having variable toughness and/or hardness

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622437A (en) * 1969-05-09 1971-11-23 Gen Dynamics Corp Composite buoyancy material
US5082726A (en) * 1989-11-01 1992-01-21 Grace N.V. Internal manifold that aids in filling molds
WO1999005447A1 (en) * 1997-07-23 1999-02-04 Cuming Corporation Subsea pipeline insulation
US6525125B1 (en) * 1999-02-05 2003-02-25 Materia, Inc. Polyolefin compositions having variable density and methods for their production and use

Also Published As

Publication number Publication date
US10676584B2 (en) 2020-06-09
EP3362506B1 (en) 2022-01-05
US20180305516A1 (en) 2018-10-25
BR112018007984B1 (pt) 2022-03-22
EP3362506A1 (en) 2018-08-22
KR20180083338A (ko) 2018-07-20
DK3362506T3 (da) 2022-01-24
PL3362506T3 (pl) 2022-05-02
BR112018007984A2 (pt) 2018-10-30
GB201518745D0 (en) 2015-12-09

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